EP0036544A1 - Method for the preparation of substituted N-azolyl-methyl-halogeno-acetanilides - Google Patents
Method for the preparation of substituted N-azolyl-methyl-halogeno-acetanilides Download PDFInfo
- Publication number
- EP0036544A1 EP0036544A1 EP81101699A EP81101699A EP0036544A1 EP 0036544 A1 EP0036544 A1 EP 0036544A1 EP 81101699 A EP81101699 A EP 81101699A EP 81101699 A EP81101699 A EP 81101699A EP 0036544 A1 EP0036544 A1 EP 0036544A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- substituted
- stage
- optionally substituted
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- -1 alkali metal salts Chemical class 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000002955 isolation Methods 0.000 claims abstract description 9
- 150000003851 azoles Chemical class 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 241000196324 Embryophyta Species 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000002363 herbicidal effect Effects 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 3
- 239000004009 herbicide Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 abstract description 10
- 239000000460 chlorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001448 anilines Chemical class 0.000 abstract description 6
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 0 C[C@]1(CC*)C=C(*)*=C*(*)=C(*=N)/C=C1 Chemical compound C[C@]1(CC*)C=C(*)*=C*(*)=C(*=N)/C=C1 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 239000000706 filtrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 235000005781 Avena Nutrition 0.000 description 4
- 244000075850 Avena orientalis Species 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 235000021506 Ipomoea Nutrition 0.000 description 4
- 241000207783 Ipomoea Species 0.000 description 4
- 241000209117 Panicum Species 0.000 description 4
- 235000006443 Panicum miliaceum subsp. miliaceum Nutrition 0.000 description 4
- 235000009037 Panicum miliaceum subsp. ruderale Nutrition 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 241000209072 Sorghum Species 0.000 description 4
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000002634 Solanum Nutrition 0.000 description 3
- 241000207763 Solanum Species 0.000 description 3
- 125000006193 alkinyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- CLEYECHXLFPJOH-UHFFFAOYSA-N n-(2,6-dimethylphenyl)ethanimine Chemical compound CC=NC1=C(C)C=CC=C1C CLEYECHXLFPJOH-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BBZPQRZKFLEVNG-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-(2,6-dimethylphenyl)methanimine Chemical compound CC1=CC=CC(C)=C1N=CC1=CC=C(Cl)C=C1 BBZPQRZKFLEVNG-UHFFFAOYSA-N 0.000 description 2
- LIBSJPJVGXUXPK-UHFFFAOYSA-N 1-cyclohex-3-en-1-yl-n-(2,6-diethylphenyl)methanimine Chemical compound CCC1=CC=CC(CC)=C1N=CC1CC=CCC1 LIBSJPJVGXUXPK-UHFFFAOYSA-N 0.000 description 2
- BRZNAYZOPMEPHN-UHFFFAOYSA-N 1h-pyrazole;sodium Chemical compound [Na].C=1C=NNC=1 BRZNAYZOPMEPHN-UHFFFAOYSA-N 0.000 description 2
- RTAMRKGXSTZINR-UHFFFAOYSA-N 2-methyl-n-phenylpropan-1-imine Chemical compound CC(C)C=NC1=CC=CC=C1 RTAMRKGXSTZINR-UHFFFAOYSA-N 0.000 description 2
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- 125000001607 1,2,3-triazol-1-yl group Chemical group [*]N1N=NC([H])=C1[H] 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/68—Halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
Definitions
- the present invention relates to a new, advantageous process for the preparation of partially known substituted N-azolylmethyl-haloacetanilides with herbicidal activity.
- reaction scheme (b) has the disadvantage that side reactions of the haloacetanilide can lead to the formation of 2,5-dioxo-1,4-diphenyl-piperazine. The yields are therefore not satisfactory in all cases.
- reaction scheme (c) has the disadvantage that it does not always run in satisfactory yields.
- the haloacetanilide of the formula (IV) has the possibility of an undesirable side reaction in that it does not attack the aniline nitrogen but acylates the free nitrogen atom of the pyrazole.
- the method according to the invention has a number of advantages. It is a widely applicable and easy to carry out three-step reaction, in which there is hardly any formation of by-products and which generally leads to good yields.
- Formula (XII) provides a general definition of the substituted N-azolylmethylhaloacetanilides which can be prepared by the process according to the invention.
- Az preferably represents the optionally substituted azolyl radicals pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1 -yl, 1,2,3,4-tetrazol-1-yl and imidazol-1-yl and for optionally substituted pyrrol-1-yl, the preferred substituents being: halogen, in particular fluorine, chlorine and bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkoxy or alkylthio each having 1 to 4 carbon atoms, phenyl, perfluoroalkyl having 1 to 4 carbon atoms, cyano, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the alkyl or al
- R preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, cycloalkenyl having 5 or 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and up to 5 identical or different halogen atoms, preferably fluorine and chlorine as halogens may be mentioned, alkoxyalkyl having 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, furthermore for straight-chain or branched alkenyl and alkynyl each having up to 6 carbon atoms, for optionally substituted phenyl, the preferred substituents being: halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having up to 2 carbon atoms and up to 3 identical or different halogen atoms such as in particular fluorine and chlorine atoms, alkoxy and alkylthio each having up to 2 carbon atoms
- X 1 , X2 and X 3 are the same or different and are preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and fluorine and chlorine.
- Hal preferably represents the halogens fluorine, chlorine and bromine.
- the new substituted N-azolylmethyl-haloacetanilides are generally defined by the formula (XIX).
- Az, X 1 , X2, X 3 and Hal preferably represent the radicals which are used in the description of the substituted N- Azolylmethyl-haloacetanilides of the formula (XII) have already been mentioned preferably for these substituents.
- R 1 preferably represents the radicals which are preferably mentioned for the substituent R, with the proviso that R 1 only represents straight-chain or branched alkyl having 1 to 8 carbon atoms if Az represents a heterocyclic radical other than pyrazole.
- Formula (XIII) provides a general definition of the anilines to be used as starting materials in carrying out stage I of the process according to the invention.
- X 1 , X 2 and X 3 preferably represent those radicals which have already been associated with the » Description of the substances of the formula (XII) which can be prepared according to the invention have preferably been mentioned for these radicals.
- anilines of the formula (XIII) are generally known compounds of organic chemistry. Examples include:
- Formula (XIV) generally defines the aldehydes to be used as starting materials for the 1st stage of the reaction according to the invention.
- R preferably represents those radicals which, in connection with the description of the substances of the formula (XII) which can be prepared according to the invention, have preferably been mentioned for these substituents.
- aldehydes of the formula (XIV) are generally known compounds of organic chemistry. Examples include:
- the azomethines of the formula (XV) formed when the first stage of the reaction according to the invention is carried out are only partially known (compare e.g. Chemical Abstracts 64, 10 760 g and 80, P 60 816 g). They are generally interesting intermediates, as are their linear and cyclic polymers.
- Formula (XVI) generally defines the haloacethalides to be used as reaction components in the second stage of the reaction according to the invention.
- shark is preferably fluorine, chlorine and bromine.
- haloacethalides of the formula (XVI) are generally known compounds of organic chemistry.
- Formula (XVIII) generally defines the azoles to be used as reactive components for the third stage of the reaction according to the invention.
- Az preferably represents those radicals which have already been mentioned for these substituents in connection with the description of the substances of the formula (XII) which can be prepared according to the invention.
- the azoles of the formula (XVIII) are generally known compounds of organic chemistry. Examples include:
- Suitable diluents for the 1st stage of the process according to the invention are all inert solvents. These preferably include alcohols, such as methanol, ethanol and tert-butanol; Ethers, such as especially tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride; and aromatic hydrocarbons, such as benzene, toluene or xylene.
- alcohols such as methanol, ethanol and tert-butanol
- Ethers such as especially tetrahydrofuran and dioxane
- halogenated hydrocarbons such as methylene chloride
- aromatic hydrocarbons such as benzene, toluene or xylene.
- the 1st stage of the process according to the invention is optionally carried out in the presence of a basic or an acidic catalyst.
- a basic or an acidic catalyst can be used here, e.g. Dimethylbenzylamine.
- Suitable acidic catalysts are in particular p-toluenesulfonic acid or acidic cation exchangers.
- reaction temperatures can be varied within a substantial range when carrying out the 1st stage of the process according to the invention. In general, temperatures between -50 and + 150 ° C, preferably between -10 and + 120 ° C.
- y ertechnischnungsmittel eligible for the 2nd stage of the process according to the invention are inert organic solvents.
- These preferably include ketones, in particular acetone and methyl ethyl ketone; Nitriles, such as in particular acetonitrile; Ethers such as tetrahydrofuran or dioxane; Esters, such as in particular ethyl acetate; halogenated hydrocarbons such as methylene chloride; and aromatic hydrocarbons such as benzene and toluene.
- reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between -20 and + 100 ° C, preferably between -20 and + 50 ° C.
- haloacethalide of the formula (XVI) are preferably used per 1 mol of azomethine of the formula (XV).
- the resulting substituted N-halomethyl-haloacetanilides are preferably reacted directly without isolation.
- Inert organic solvents are used as diluents for the third stage of the process according to the invention in question. These preferably include the solvents already mentioned in the 2nd stage.
- acid binders can be used as acid binders. These preferably include alkali carbonates, such as sodium and potassium carbonate or sodium hydrogen carbonate; also lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines, such as triethylamine, dimethylbenzylamine and pyridine. However, it is also possible to use a corresponding excess of azole or to use the azole in the form of an alkali metal salt.
- alkali carbonates such as sodium and potassium carbonate or sodium hydrogen carbonate
- lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines such as triethylamine, dimethylbenzylamine and pyridine.
- reaction temperatures can be varied over a wide range when carrying out the third stage of the process according to the invention. In general, temperatures between -20 and + 100 ° C, preferably between -10 and + 80 ° C.
- the process according to the invention can also be carried out as a one-pot reaction.
- the active compounds of the formula (XII) which can be prepared according to the invention are notable for very good herbicidal, in particular selective, herbicidal activity which is comparable to that of the known 2,6-diethyl-N-methoxymethylchloroacetanilide (cf. Pest Control, Volume 5, page 255, Springer-Verlag (1977)) is superior (compare the following example A).
- the active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
- the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover.
- the compounds for weed control in permanent crops for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.
- the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances, fine encapsulation in polymeric substances.
- formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.
- extenders that is to say liquid solvents and / or solid carriers
- surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
- water e.g. organic solvents can also be used as auxiliary solvents.
- aromatics such as xylene, toluene, or alkylnaphthalenes
- chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride
- aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
- strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
- Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular and latex-shaped polymers, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
- Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
- the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
- the active compounds according to the invention can be applied both before and after emergence of the plants. It is preferably used before the plants emerge, that is to say in the pre-emergence process. They can also be worked into the soil before sowing.
- the amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect you want. In general, the application rates are between 0.05 and 10 kg of active ingredient per ha, preferably between 0.1 and 5 kg / ha.
- Example A The effect and possible uses of the substances according to the invention for weed control are shown in Example A.
- stage 2 The reaction mixture obtained in stage 2 is added to a solution of 170 g (2.5 mol) of pyrazole and 250 ml of methylene chloride at 20 to 30 ° C. with stirring within 30 minutes. When the addition is complete, the mixture is stirred for 4 hours at room temperature. The reaction mixture is then added to a saturated solution of sodium hydrogen carbonate. The organic phase is separated off, washed several times with saturated sodium bicarbonate solution and dried over sodium sulfate and concentrated by distilling off the solvent. The remaining residue is recrystallized from toluene / ligroin. This gives 122.5 g (42% of theory, based on the aniline used in stage 1) of N- (1-pyrazol-1-yl-isobut-1-yl) chloroacetanilide, melting point 75 ° C.
- active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
- the active ingredients (XII-1) and (X V -7) which can be prepared according to the invention show a better selective activity than the substance (A) known from the prior art.
Abstract
Description
Die vorliegende Erfindung betrifft ein neues, vorteilhaftes Verfahren zur Herstellung von teilweise bekannten substituierten N-Azolylmethyl-halogenacetaniliden mit herbizider Wirksamkeit.The present invention relates to a new, advantageous process for the preparation of partially known substituted N-azolylmethyl-haloacetanilides with herbicidal activity.
Es ist bereits bekannt geworden, daß man bestimmte N-Azolylmethylhalogenacetanilide erhalten kann, wenn man Aniline mit Paraformaldehyd in Gegenwart katalytischer Mengen Kaliumhydroxid umsetzt, die entstehenden Phenylazomethine mit einem Halogenacethalogenid versetzt (vergleiche US-Patentschriften 3 630 716 und 3 637 847) und die entstehenden N-Halogenmethyl-a-halogenacetanilide mit entsprechenden Heterocyclen gegebenenfalls in Gegenwart eines Säurebindemittels und in Gegenwart eines inerten organischen Lösungsmittels bei Temperaturen zwischen 0°C und 200°C gemäß folgendem Reaktionsschema (a) umsetzt (vgl. US-PS 3 630 716, US-PS 3 637 847, DE-OS 2 648 008 und DE-OS 2 704 281):
- Az' =über ein Ringstickstoffatom gebundener N-haltiger heterocyclischer Ring;
- X'1,X'2,X'3=Wasserstoff,Alkyl,Alkoxy,Halogenalkyl,Alkoxyalkyl, u.a., wobei X'1 ,X'2 und X'3 gleichartig oder verschieden sind;
- Hal' =Halogen.
- A z '= N-containing heterocyclic ring bonded via a ring nitrogen atom;
- X ' 1 , X' 2 , X ' 3 = hydrogen, alkyl, alkoxy, haloalkyl, alkoxyalkyl, among others, where X' 1 , X ' 2 and X' 3 are identical or different;
- Hal '= halogen.
Weiterhin ist bereits die Herstellung solcher Verbindungen der Formel (VII) bekannt geworden, in denen die Methylengruppe des Azolylmethyl-Restes substituiert ist (vgl. DE-OS 2 835 156 und DE-OS 2 835 157). So lassen sich derartige substituierte N-Pyrazölylmethylhalogen-acetanilide der Formel (X) erhalten, wenn man Halogenacetanilide der Formel (VIII) mit entsprechenden Pyrazol-Derivaten in Gegenwart eines Säurebinders, wie beispielsweise eines Alkalihydroxids, und gegebenenfalls in Gegenwart eines inerten organischen Lösungsmittels bei Temperaturen zwischen -70°C und +100°C nach folgendem Reaktionsschema (b) umsetzt:
- R' =Alkyl,Cycloalkyl,Halogenalkyl,Alkoxyalkyl, Alkenyl, Alkinyl, gegebenenfalls substituiertes Phenyl;
- R'1 ,R'2 ,R'3= Wasserstoff,Alkyl,Halogen,Alkoxy, wobei R'1 , R'2 und R'3 gleichartig oder verschieden sind ;
- Y' = Halogen, Mesylat- oder Tosylat-Rest;
- X'1 ,X'2 ,X'3 und Hal' = Bedeutung wie oben angegeben.
- R '= alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, optionally substituted phenyl;
- R ' 1 , R' 2 , R ' 3 = hydrogen, alkyl, halogen, alkoxy, where R' 1 , R ' 2 and R' 3 are identical or different;
- Y '= halogen, mesylate or tosylate residue;
- X ' 1 , X' 2 , X ' 3 and Hal' = meaning as stated above.
Dieses Verfahren gemäß Reaktionsschema (b) hat jedoch den Nachteil, daß Nebenreaktionen des Halogenacetanilids zur Bildung von 2,5-Dioxo-1,4-diphenyl-piperazin führen können. Die Ausbeuten sind somit nicht in allen Fällen befriedigend.However, this process according to reaction scheme (b) has the disadvantage that side reactions of the haloacetanilide can lead to the formation of 2,5-dioxo-1,4-diphenyl-piperazine. The yields are therefore not satisfactory in all cases.
Die substituierten N-Pyrazolylmethyl-halogenacetanilide der Formel (X) können auch hergestellt werden, indem man Aniline der Formel (I) zunächst mit Pyrazolyl-Derivaten der Formel (IX) in Gegenwart eines Säurebinders, wie insbesondere einem Ueberschuß an Anilin, umsetzt und anschließend die erhaltenen Aniline der Formel (XI) mit einem Halogenacethalogenid der Formel (IV) in Gegenwart eines inerten organischen Lösungsmittels, wie beispielsweise Toluol oder Dimethylformamid, gegebenenfalls in Gegenwart eines Säurebindemittels, wie z.B. Kaliumcarbonat, bei Temperaturen zwischen 20 und 1000C gemäß folgendem Reaktionsschema (c) umsetzt:
Dieses Verfahren gemäß Reaktionsschema (c) hat jedoch den Nachteil, daß es nicht immer in befriedigenden Ausbeuten abläuft. Das Halogenacetanilid der Formel (IV) hat die Möglichkeit zu einer unerwünschten Nebenreaktion, indem es nicht am Anilinstickstoff angreift, sondern das freie Stickstoffatom des Pyrazols acyliert.However, this process according to reaction scheme (c) has the disadvantage that it does not always run in satisfactory yields. The haloacetanilide of the formula (IV) has the possibility of an undesirable side reaction in that it does not attack the aniline nitrogen but acylates the free nitrogen atom of the pyrazole.
Es wurde nun gefunden, daß man substituierte N-Azolyl- methyl-halogenacetanilide der Formel
- Az für einen über ein Stickstoffatom gebundenen, gegebenenfalls substituierten N-haltigen heterocyclischen Rest steht,
- R für Alkyl, Cycloalkyl, Cycloalkenyl, Halogenalkyl, Alkoxyalkyl, Alkenyl, Alkinyl, gegebenenfalls substituiertes Phenyl oder einen gegebenenfalls substituierten heteroaromatischen Rest steht,
- X',X2 und X3 gleich oder verschieden sind und für Wasserstoff, Alkyl oder Halogen stehen und
- Hal für Halogen steht,
erhält, wenn man in einer 1.Stufe Aniline der Formel
- X1,X2 und X3 die oben angegebene Bedeutung haben,
mit Aldehyden der Formel
- R die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines basischen oder sauren Katalysators umsetzt, dann in einer 2. Stufe die entstehenden Azomethine der Formel
- R,X1,X2und X3 die oben angegebene Bedeutung haben,
mit Halogenacethalogeniden der Formel
- Hal die oben angegebene Bedeutung hat,
gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und in einer 3. Stufe die entstehenden substituierten N-Halogenmethyl-halogenacetanilide der Formel
- R,X1 ,X2 ,X3 und Hal die oben angegebene Bedeutung haben,
direkt, oder gegebenenfalls nach vorheriger Isolierung, mit Azolen der Formel
- Az die oben angegebene Bedeutung hat,
gegebenenfalls in Gegenwart eines Verdünnungsmittels. und in Gegenwart eines Säurebindemittels umsetzt, wobei die Azole der Formel (XVIII) auch in Form ihrer Alkalimetallsalze eingesetzt werden können.It has now been found that substituted N-azolylmethylhaloacetanilides of the formula
- Az represents an optionally substituted N-containing heterocyclic radical bonded via a nitrogen atom,
- R represents alkyl, cycloalkyl, cycloalkenyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, optionally substituted phenyl or an optionally substituted heteroaromatic radical,
- X ', X 2 and X 3 are the same or different and represent hydrogen, alkyl or halogen and
- Hal stands for halogen,
is obtained if you have aniline of the formula in a 1st stage
- X 1 , X 2 and X 3 have the meaning given above,
with aldehydes of the formula
- R has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a basic or acidic catalyst, then in a second stage the resulting azomethines of the formula
- R, X 1 , X 2 and X 3 have the meaning given above,
with haloacethalides of the formula
- Hal has the meaning given above,
if appropriate in the presence of a diluent and in a third stage the resulting substituted N-halomethyl-haloacetanilides of the formula
- R, X 1 , X 2 , X 3 and Hal have the meaning given above,
directly, or optionally after prior isolation, with azoles of the formula
- Az has the meaning given above,
optionally in the presence of a diluent. and in the presence of an acid binder, the azoles of the formula (XVIII) also being able to be used in the form of their alkali metal salts.
Es ist als ausgesprochen überraschend zu bezeichnen, daß das erfindungsgemäße Verfahren in guten Ausbeuten verläuft. Aufgrund der hohen llethylenaktivität der Aldehyde der Formel (XIV) wäre in der 1. Stufe der erfindungsgemäBen Umsetzung eine Aldolkondensation zu höher kondensierten Derivaten möglich gewesen (vergleiche hierzu auch Chem. Rev. 26, 297 - 333 (1940)). Außerdem wäre in der 3.Stufe der erfindungsgemäßen Umsetzung eine Dehydrohalogenierungs-Reaktion an den substituierten N-Halogenmethyl-halogenacetaniliden der Formel (XVII) zu erwarten gewesen.It can be described as extremely surprising that the process according to the invention proceeds in good yields. Due to the high ethylene activity of the aldehydes of the formula (XIV), an aldol condensation to more highly condensed derivatives would have been possible in the 1st stage of the reaction according to the invention (see also Chem. Rev. 26, 297-333 (1940)). In addition, a dehydrohalogenation reaction on the substituted N-halomethylhaloacetanilides of the formula (XVII) would have been expected in the third stage of the reaction according to the invention.
Das erfindungsgemäße Verfahren weist eine Reihe von Vorteilen auf. Es handelt sich um eine breit anwendbare und einfach durchführbare Dreistufenreaktion, bei der es kaum zur Bildung von Nebenprodukten kommt und die allgemein zu guten Ausbeuten führt.The method according to the invention has a number of advantages. It is a widely applicable and easy to carry out three-step reaction, in which there is hardly any formation of by-products and which generally leads to good yields.
Die nach dem erfindungsgemäßen Verfahren herstellbaren substituierten N-Azolylmethyl-halogenacetanilide der Formel (XII) sind teilweise bekannt (vgl. DE-OS 2 835 156 und DE-OS 2 835 157).The substituted N-azolylmethylhaloacetanilides of the formula (XII) which can be prepared by the process according to the invention are known in some cases (cf. DE-OS 2 835 156 and DE-OS 2 835 157).
Noch nicht bekannt sind die substituierten N-Azolyl- methyl-halogenacetanilide der Formel
- Az für einen über ein Stickstoffatom gebundenen, gegebenenfalls substituierten N-haltigen heterocyclischen Rest steht,
- R1 für Cycloalkyl, Cycloalkenyl, Halogenalkyl, Alkoxyalkyl,Alkenyl,Alkinyl, gegebenenfalls substituiertes Phenyl oder einen gegebenenfalls substituierten heteroaromatischen Rest steht, sowie zusätzlich für Alkyl steht, wenn Az für einen anderen heterocyclischen Rest als Pyrazol steht,
- X1,X2 und X3 gleich oder verschieden sind und für Wasserstoff, Alkyl oder Halogen stehen und
- Hal für Halogen steht.
- Az represents an optionally substituted N-containing heterocyclic radical bonded via a nitrogen atom,
- R 1 represents cycloalkyl, cycloalkenyl, haloalkyl, alkoxyalkyl, alkenyl, alkynyl, optionally substituted phenyl or an optionally substituted heteroaromatic radical, and additionally stands for alkyl if Az stands for a heterocyclic radical other than pyrazole,
- X 1 , X 2 and X 3 are the same or different and represent hydrogen, alkyl or halogen and
- Hal stands for halogen.
Die nach dem erfindungsgemäßen Verfahren herstellbaren substituierten N-Azolylmethyl-halogenacetanilide sind durch die Formel (XII) allgemein definiert. In dieser Formel steht Az vorzugsweise für die gegebenenfalls substituierten Azolylreste Pyrazol-1-yl, 1,2,4-Triazol-1-yl, 1,2,3-Triazol-1-yl, 1,3,4-Triazol-1-yl, 1,2,3,4-Tetrazol-1-yl und Imidazol-1-yl sowie für gegebenenfalls substituiertes Pyrrol-1-yl, wobei als Substituenten vorzugsweise infrage kommen: Halogen, insbesondere Fluor, Chlor und Brom, geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy oder Alkylthio mit jeweils 1 bis 4 Kohlenstoffatomen, Phenyl, Perfluoralkyl mit 1 bis 4 Kohlenstoffatomen, Cyano, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 4 Kohlenstoffatomen im Alkyl- bzw. im Alkoxy-Teil sowie Hydroxycarbonyl.Formula (XII) provides a general definition of the substituted N-azolylmethylhaloacetanilides which can be prepared by the process according to the invention. In this formula, Az preferably represents the optionally substituted azolyl radicals pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1 -yl, 1,2,3,4-tetrazol-1-yl and imidazol-1-yl and for optionally substituted pyrrol-1-yl, the preferred substituents being: halogen, in particular fluorine, chlorine and bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkoxy or alkylthio each having 1 to 4 carbon atoms, phenyl, perfluoroalkyl having 1 to 4 carbon atoms, cyano, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the alkyl or alkoxy part and also hydroxycarbonyl.
R steht vorzugsweise für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Kohlenstoffatomen, Cycloalkyl mit 3 bis 6 Kohlenstoffatomen Cycloalkenyl mit 5 oder '6 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und bis zu 5 gleichen oder verschiedenen Halogenatomen, wobei als Halogene vorzugsweise Fluor und Chlor genannt seien, Alkoxyalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil und 1 bis 4 Kohlenstoffatomen im Alkoxyteil, ferner für geradkettiges oder verzweigtes Alkenyl und Alkinyl mit jeweils bis zu 6 Kohlenstoffatomen, für gegebenenfalls substituiertes Phenyl, wobei als Substituenten vorzugsweise in Frage kommen: Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit bis zu 2 Kohlenstoffatomen und bis zu 3 gleichen oder verschiedenen Halogenatomen, wie insbesondere Fluor- und Chloratomen, Alkoxy und Alkylthio mit jeweils bis zu 2 Kohlenstoffatomen, Cyano und Nitro; sowie für einen gegebenenfalls substituierten 5- oder 6-gliedrigen heteroaromatischen Rest mit einem oder mehreren Heteroatomen, wie Sauerstoff, Schwefel und Stickstoff, beispielsweise seien genannt: Furan, Thiophen sowie die für Az vorzugsweise genannten Azolylreste, wobei als Substituienten infrage kommen: Alkyl mit 1 bis 4 Kohlenstoffatomen, Halogen, Halogenalkyl mit bis zu 2 Kohlenstoff- und bis zu 3 gleichen oder verschiedenen Halogenatomen, wie insbesondere Fluor- und Chloratomen, Alkoxy und Alkylthio mit jeweils bis zu 2 Kohlenstoffatomen.R preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, cycloalkenyl having 5 or 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and up to 5 identical or different halogen atoms, preferably fluorine and chlorine as halogens may be mentioned, alkoxyalkyl having 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy part, furthermore for straight-chain or branched alkenyl and alkynyl each having up to 6 carbon atoms, for optionally substituted phenyl, the preferred substituents being: halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having up to 2 carbon atoms and up to 3 identical or different halogen atoms such as in particular fluorine and chlorine atoms, alkoxy and alkylthio each having up to 2 carbon atoms, cyano and nitro; and for an optionally substituted 5- or 6-membered heteroaromatic radical with one or more heteroatoms, such as oxygen, sulfur and nitrogen, examples may be mentioned: furan, thiophene and the azolyl radicals preferably mentioned for Az, the following being suitable as substituents: alkyl having 1 up to 4 carbon atoms, halogen, haloalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms, such as in particular fluorine and chlorine atoms, alkoxy and alkylthio each with up to 2 carbon atoms.
X1, X2 und X3sind gleich oder verschieden und stehen vorzugsweise für Wasserstoff, geradkettiges oder verzweigtes Alkyl mit 1 bis 4 Kohlenstoffatomen sowie für Fluor und Chlor.X 1 , X2 and X 3 are the same or different and are preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and fluorine and chlorine.
Hal steht vorzugsweise für die Halogene Fluor, Chlor und Brom.Hal preferably represents the halogens fluorine, chlorine and bromine.
Die neuen substituierten N-Azolylmethyl-halogenacetanilide sind durch die Formel (XIX) allgemein definiert. In dieser Formel stehen Az, X1 , X2, X3 und Hal vorzugsweise für die Reste, die bei der Beschreibung der substituierten N-Azolylmethyl-halogenacetanilide der Formel (XII) bereits vorzugsweise für diese Substituenten genannt wurden. R1 steht vorzugsweise für die für den Substituenten R vorzugsweise genannten Reste, mit der Maßgabe, daß R1 nur dann für geradkettiges oder verzweigtes Alkyl mit 1 bis 8 Kohlenstoffatomen steht, wenn Az für einen anderen heterocyclischen Rest als Pyrazol steht.The new substituted N-azolylmethyl-haloacetanilides are generally defined by the formula (XIX). In this formula, Az, X 1 , X2, X 3 and Hal preferably represent the radicals which are used in the description of the substituted N- Azolylmethyl-haloacetanilides of the formula (XII) have already been mentioned preferably for these substituents. R 1 preferably represents the radicals which are preferably mentioned for the substituent R, with the proviso that R 1 only represents straight-chain or branched alkyl having 1 to 8 carbon atoms if Az represents a heterocyclic radical other than pyrazole.
Verwendet man beispielsweise 2,6-Dimethylanilin und Acetaldehyd als Ausgangsstoffe und Chloracetylchlorid sowie Pyrazol als Reaktionskomponenten, so kann der Ablauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema wiedergegeben werden:
Die bei der Durchführung der I.Stufe des erfindungsgemäßen Verfahrens als Ausgangsstoffe zu verwendenden Aniline sind durch die Formel (XIII) allgemein definiert. In dieser Formel stehen X1, X2 und X3 vorzugsweise für diejenigen Reste, die bereits im Zusammenhang mit der » Beschreibung der erfindungsgemäß herstellbaren Stoffe der Formel (XII) vorzugsweise für diese Reste genannt wurden.Formula (XIII) provides a general definition of the anilines to be used as starting materials in carrying out stage I of the process according to the invention. In this formula, X 1 , X 2 and X 3 preferably represent those radicals which have already been associated with the » Description of the substances of the formula (XII) which can be prepared according to the invention have preferably been mentioned for these radicals.
Die Aniline der Formel (XIII) sind allgemein bekannte Verbindungen der organischen Chemie. Als Beispiele seien genannt:
Die außerdem für die 1.Stufe der erfindungsgemäßen Umsetzung als Ausgangsstoffe zu verwendenden Aldehyde sind durch die Formel (XIV) allgemein definiert. In dieser Formel steht R vorzugsweise für diejenigen Reste, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäß herstellbaren Stoffe der Formel (XII) vorzugsweise für diesen Substituenten genannt wurden.Formula (XIV) generally defines the aldehydes to be used as starting materials for the 1st stage of the reaction according to the invention. In this formula, R preferably represents those radicals which, in connection with the description of the substances of the formula (XII) which can be prepared according to the invention, have preferably been mentioned for these substituents.
Die Aldehyde der Formel (XIV) sind allgemein bekannte Verbindungen der organischen Chemie. Als Beispiele seien genannt:
Die bei der Durchführung der 1. Stufe der erfindungsgemäßen Umsetzung entstehenden Azomethine der Formel (XV) sind nur teilweise bekannt (vergleiche z.B. Chemical Abstracts 64, 10 760 g und 80, P 60 816 g). Sie sind allgemein interessante Zwischenprodukte, ebenso wie ihre linearen und cyclischen Polymeren.The azomethines of the formula (XV) formed when the first stage of the reaction according to the invention is carried out are only partially known (compare e.g. Chemical Abstracts 64, 10 760 g and 80, P 60 816 g). They are generally interesting intermediates, as are their linear and cyclic polymers.
Die in der 2. Stufe der erfindungsgemäßen Umsetzung als Reaktionskomponenten zu verwendenden Halogenacethalogenide sind durch die Formel (XVI) allgemein definiert. In dieser Formel steht Hai vorzugsweise für Fluor, Chlor und Brom.Formula (XVI) generally defines the haloacethalides to be used as reaction components in the second stage of the reaction according to the invention. In this formula, shark is preferably fluorine, chlorine and bromine.
Die Halogenacethalogenide der Formel (XVI) sind allgemein bekannte Verbindungen der organischen Chemie.The haloacethalides of the formula (XVI) are generally known compounds of organic chemistry.
Die bei der Durchführung der 2.Stufe der erfindungsgemäßen Umsetzung entstehenden substituierten N-Halogenmethyl-halogenacetanilide der Formel (XVII) sind noch nicht bekannt. Sie stellen allgemein interessante Zwischenprodukte dar. Als Beispiele seien genannt:
Die außerdem für die 3.Stufe der erfindungsgemäßen Umsetzung als Reakticnskcnponenten zu verwendenden Azole sind durch die Formel (XVIII) allgemein definiert. In dieser Formel steht Az vorzugsweise für diejenigen Reste, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäß herstellbaren Stoffe der Formel (XII) vorzugsweise für diesen Substituenten genannt wurden.Formula (XVIII) generally defines the azoles to be used as reactive components for the third stage of the reaction according to the invention. In this formula, Az preferably represents those radicals which have already been mentioned for these substituents in connection with the description of the substances of the formula (XII) which can be prepared according to the invention.
Die Azole der Formel (XVIII) sind allgemein bekannte Verbindungen der organischen Chemie. Als Beispiele seien genannt:
Als Verdünnungsmittel kommen für die 1.Stufe des erfindungsgemäßen Verfahrens alle inerten Lösungsmittel infrage. Hierzu gehören vorzugsweise Alkohole, wie Methanol, Ethanol und tert.-Butanol; Ether, wie insbesondere Tetrahydrofuran und Dioxan; halogenierte Kohlenwasserstoffe, wie Methylenchlorid; sowie aromatische Kohlenwasserstoffe, wie Benzol, Toluol oder Xylol.Suitable diluents for the 1st stage of the process according to the invention are all inert solvents. These preferably include alcohols, such as methanol, ethanol and tert-butanol; Ethers, such as especially tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride; and aromatic hydrocarbons, such as benzene, toluene or xylene.
Die 1. Stufe des erfindungsgemäßen Verfahrens wird gegebenenfalls in Gegenwart eines basischen oder eines sauren Katalysators durchgeführt. Hierbei können alle üblichen basischen Katalysatoren eingesetzt werden, wie z.B. Dimethylbenzylamin. Als saure Katalysatoren kommen insbesondere p-Toluolsulfonsäure oder saure Kationenaustauscher in Betracht.The 1st stage of the process according to the invention is optionally carried out in the presence of a basic or an acidic catalyst. All common basic catalysts can be used here, e.g. Dimethylbenzylamine. Suitable acidic catalysts are in particular p-toluenesulfonic acid or acidic cation exchangers.
Die Reaktionstemperaturen können bei der Durchführung der 1. Stufe des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -50 und +150°C, vorzugsweise zwischen -10 und +120°C.The reaction temperatures can be varied within a substantial range when carrying out the 1st stage of the process according to the invention. In general, temperatures between -50 and + 150 ° C, preferably between -10 and + 120 ° C.
Bei der Durchführung der 1.Stufe des erfindungsgemäßen Verfahrens setzt man vorzugsweise auf 1 Mol Anilin der Formel (XIII) 1 bis 2 Mol Aldehyd der Formel (XIV) und gegebenenfalls 0,01 bis 0,1 Mol Katalysator ein. Das entstehende Reaktionswasser wird in üblicher Art und Weise entfernt, wie z.B. durch Zugabe wasserentziehender Mittel, beispielsweise Natriumsulfat oder Magnesiumsulfat oder durch physikalische Methoden, wie z.B. Erhitzen am Wasserabscheider, azeotrope Destillation gegebenenfalls im Vakuum oder auch Ausfrieren. Die Isolierung der Azomethine der Formel (XV) erfolgt in üblicher Weise.When carrying out the 1st stage of the process according to the invention, 1 to 2 mol of aldehyde of the formula (XIV) and, if appropriate, 0.01 to 0.1 mol of catalyst are preferably used per 1 mol of aniline of the formula (XIII). The water of reaction formed is removed in a conventional manner, e.g. by adding dehydrating agents, e.g. sodium sulfate or magnesium sulfate, or by physical methods, e.g. Heating on a water separator, azeotropic distillation if necessary in a vacuum or freezing out. The azomethines of the formula (XV) are isolated in the customary manner.
Als yerdünnungsmittel kommen für die 2.Stufe des erfindungsgemäßen Verfahrens inerte organische Lösungsmittel infrage. Hierzu gehören vorzugsweise Ketone, wie insbesondere Aceton und Methylethylketon; Nitrile, wie insbesondere Acetonitril; Ether, wie Tetrahydrofuran oder Dioxan; Ester, wie insbesondere Essigester; halogenierte Kohlenwasserstoffe, wie Methylenchlorid; sowie aromatische Kohlenwasserstoffe, wie Benzol und Toluol.When y erdünnungsmittel eligible for the 2nd stage of the process according to the invention are inert organic solvents. These preferably include ketones, in particular acetone and methyl ethyl ketone; Nitriles, such as in particular acetonitrile; Ethers such as tetrahydrofuran or dioxane; Esters, such as in particular ethyl acetate; halogenated hydrocarbons such as methylene chloride; and aromatic hydrocarbons such as benzene and toluene.
Die Reaktionstemperaturen können bei der Durchführung der 2. Stufe des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20 und +100°C, vorzugsweise zwischen -20 und +50°C.The reaction temperatures can be varied within a substantial range when carrying out the second stage of the process according to the invention. In general, temperatures between -20 and + 100 ° C, preferably between -20 and + 50 ° C.
Bei der Durchführung der 2.Stufe des erfindungsgemäßen Verfahrens setzt man vorzugsweise auf 1 Mol Azomethin der Formel (XV) 1 bis 1,5 Mol Halogenacethalogenid der Formel (XVI) ein. Die entstehenden substituierten N-Halogenmethyl-halogenacetanilide werden vorzugsweise ohne Isolierung direkt weiter umgesetzt.When carrying out the second stage of the process according to the invention, 1 to 1.5 mol of haloacethalide of the formula (XVI) are preferably used per 1 mol of azomethine of the formula (XV). The resulting substituted N-halomethyl-haloacetanilides are preferably reacted directly without isolation.
Als Verdünnungsmittel kommen für die 3.Stufe des erfindungsgemäßen Verfahrens inerte organischen Lösungsmittel infrage. Hierzu gehören vorzugsweise die bei der 2.Stufe bereits vorzugsweise genannten Solventien.Inert organic solvents are used as diluents for the third stage of the process according to the invention in question. These preferably include the solvents already mentioned in the 2nd stage.
Als Säurebindemittel können alle üblicherweise verwendbaren anorganischen und organischen Säureakzeptoren eingesetzt werden. Hierzu gehören vorzugsweise Alkalicarbonate, wie Natrium- und Kaliumcarbonat oder Natriumhydrogencarbonat; ferner niedere tertiäre Alkylamine, Aralkylamine, aromatische Amine oder Cycloalkylamine, wie Triethylamin, Dimethylbenzylamin und Pyridin. Es ist aber auch möglich, einen entsprechenden Ueberschuß an Azol zu verwenden, bzw. das Azol in Form eines Alkalimetallsalzes einzusetzen.All commonly used inorganic and organic acid acceptors can be used as acid binders. These preferably include alkali carbonates, such as sodium and potassium carbonate or sodium hydrogen carbonate; also lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines, such as triethylamine, dimethylbenzylamine and pyridine. However, it is also possible to use a corresponding excess of azole or to use the azole in the form of an alkali metal salt.
' Die Reaktionstemperaturen können bei der Durchführung der 3. Stufe des erfindungsgemäßen Verfahrens in einem grösseren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20 und +100°C, vorzugsweise zwischen -10 und +80°C.The reaction temperatures can be varied over a wide range when carrying out the third stage of the process according to the invention. In general, temperatures between -20 and + 100 ° C, preferably between -10 and + 80 ° C.
Bei der Durchführung der 3.Stufe des erfindungsgemäßen Verfahrens setzt man auf 1 Mol substituiertes N-Halogenmethyl-halogenacetanilid der Formel (XVII) 1 bis 2,5 Mol Azol der Formel (XVIII) und 1 Mol Säurebinder ein. Die Isolierung der Endprodukte erfolgt in allgemein üblicher Art und Weise.When carrying out the third stage of the process according to the invention, 1 to 2.5 moles of azole of the formula (XVIII) and 1 mole of acid binder are employed per mole of substituted N-halomethylhaloacetanilide of the formula (XVII). The end products are isolated in a generally customary manner.
Das erfindungsgemäße Verfahren läßt sich auch als Eintopf-Reaktion durchführen.The process according to the invention can also be carried out as a one-pot reaction.
Die erfindungsgemäß herstellbaren Wirkstoffe der Formel (XII) zeichnen sich durch sehr gute herbizide, insbesondere selektiv-herbizide Wirksamkeit aus, die der dem bekannten 2,6-Diethyl-N-methoxymethyl-chloracetanilid (vgl.R.Wegler, Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel, Band 5, Seite 255, Springer-Verlag (1977)) überlegen ist (vergleiche das folgende Beispiel A).The active compounds of the formula (XII) which can be prepared according to the invention are notable for very good herbicidal, in particular selective, herbicidal activity which is comparable to that of the known 2,6-diethyl-N-methoxymethylchloroacetanilide (cf. Pest Control, Volume 5, page 255, Springer-Verlag (1977)) is superior (compare the following example A).
Die erfindungsgemäßen Wirkstoffe beeinflussen das Pflanzenwachstum und können deshalb als Defoliants, Desiccants, Krautabtötungsmittel, Keimhemmungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden. Unter Unkraut im weitesten Sinne sind alle Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selektive Herbizide wirken, hängt im wesentlichen von der angewendeten Menge ab.The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden:
- Dikotyle Unkräuter der Gattungen: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
- Dicotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbitä.
- Monokotyle Unkräuter der Gattungen: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon,Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dac-tyloctenium, Agrostis, Alopecurus, Apera.
- Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
- Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
- Dicotyle cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
- Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasemirumum, Scalumum, Scalumumum , Sphenoclea, Dac-tyloctenium, Agrostis, Alopecurus, Apera.
- Monocot cultures of the genera: Oryza, Zea, Triticum, hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen z.B. Forst-, Ziergehölz-, Obst-, Wein-, Citrus-, Nuss-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht-.und Hopfenanlagen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden. Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsionskonzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe, Feinverkapselungen in polymeren Stoffen.Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops. The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances, fine encapsulation in polymeric substances.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/ oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser.These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage:
- z.B. natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier-und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol- Äther, z.B. Alkylarylpolyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.
- For example, natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Possible solid carriers for granules are: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made from organic materials such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige und latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular and latex-shaped polymers, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo-Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen O,5 und 90 %. :
- Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Verwendung finden, wobei Fertigformulierung oder Tankmischung möglich ist. Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Wuchsstoffen, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln ist möglich.
- The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides for weed control, finished formulation or tank mixing being possible. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder der daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Streuen.The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden. Die Anwendung wird vorzugsweise vor dem Auflaufen der Pflanzen, also im pre-emergence-Verfahren, vorgenommen. Sie können auch vor der Saat in den Boden eingearbeitet werden.The active compounds according to the invention can be applied both before and after emergence of the plants. It is preferably used before the plants emerge, that is to say in the pre-emergence process. They can also be worked into the soil before sowing.
Die angewandte Wirkstoffmenge kann in größeren Bereichen schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effekts ab. Im allgemeinen liegen die Aufwandmengen zwischen 0,05 und 10 kg Wirkstoff pro ha, vorzugsweise zwischen 0,1 und 5 kg/ha.The amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect you want. In general, the application rates are between 0.05 and 10 kg of active ingredient per ha, preferably between 0.1 and 5 kg / ha.
Wirkung und Einsatzmöglichkeiten der erfindungsgemäßen Stoffe zur Unkrautbekämpfung gehen aus dem Beispiel A hervor.The effect and possible uses of the substances according to the invention for weed control are shown in Example A.
Das erfindungsgemäße Verfahren sei anhand der folgenden Herstellungsbeispiele erläutert.The process according to the invention is explained using the following production examples.
Zu der in der Stufe 2 erhaltenen Reaktionsmischung werden 170g(2,5 Mol) Pyrazol gegeben, wobei die Temperatur unter 0°C gehalten wird. Durch Zugabe von ca. 300 ml Toluol bleibt die Reaktionsmischung gut rührbar. Man läßt auf Raumtemperatur erwärmen und rührt 3 Stunden nach. Anschließend wird das Reaktionsgemisch in 1000 ml einer bei 20°C gesättigten, wässrigen Natriumhydrogencarbonatlösung gegeben, die organische Phase wird abgetrennt und filtriert. Das Filtrat wird mehrmals mit gesättigter Natriumhydrogencarbonatlösung gewaschen, über Natriumsulfat getrocknet und im Vakuum eingeengt. Das zurückbleibende Oel wird aus 300 ml Ligroin umkristallisiert. Man erhält 198g (68% der Theorie, bezogen auf in Stufe 2 eingesetztes N-Ethyliden-2,6-dimethylanilin) 2,6-Dimethyl-N-(1-pyrazol-1-yl-eth-l-yl)-chloracetanilid vom Schmelzpunkt 90°C.
Zu der in der Stufe 2 erhaltenen Reaktionsmischung wird bei -15 bis -10°C eine Lösung von 14,3g (0,21 Mol) Pyrazol und 21,2g (0,21 Mol) Triethylamin in 150 ml absolutem Acetonitril getropft und anschließend 4 Stun'- den bei Raumtemperatur gerührt, abgesaugt und das Filtrat eingeengt. Der Rückstand wird aus Diisopropylether/Essigsäureethylester umkristallisiert. Man erhält 62,5 g (81 % der Theorie) 2,6-Diethyl-N-(cyclohexen-3-yl- pyrazol-l-yl-methyl)-chloracetanilid vom Schmelzpunkt 111°C.A solution of 14.3 g (0.21 mol) of pyrazole and 21.2 g (0.21 mol) of triethylamine in 150 ml of absolute acetonitrile is added dropwise to the reaction mixture obtained in stage 2 at -15 to -10 ° C. and then 4 Stir'- at room temperature, suction filtered and the filtrate was concentrated. The residue is recrystallized from diisopropyl ether / ethyl acetate. 62.5 g (81% of theory) of 2,6-diethyl-N- (cyclohexen-3-yl-pyrazol-1-yl-methyl) -chloroacetanilide with a melting point of 111 ° C. are obtained.
Zu 36,6g (0,15 Mol) N-(4-Chlorbenzyliden)-2,6-dimethylanilin in 110 ml Acetonitril werden bei -20 bis -15°C 20g (0,177 Mol) Chloracetylchlorid getropft und 25 Minuten bei -15 bis -10°C gerührt. Das dabei anfallende 2,6-Dimethyl-N-(chlor-4-chlorphenyl-methyl)-chloracetanilid wird ohne Isolierung direkt weiter umgesetzt.
Zu der in der Stufe 2 erhaltenen Reaktionsmischung wird bei -15°C bis -10°C eine feine Suspension von 18g Natriumpyrazol in 270ml trockenem Acetonitril getropft. Anschlies- send wird 4 Stunden bei Raumtemperatur gerührt, abgesaugt und das Filtrat eingeengt. Der Rückstand wird aus n-Hexan/ Diisopropylether umkristallisiert. Man erhält 46,2g (79 % der Theorie) 2,6-Dimethyl-N-(4-chlorphenyl-pyrazol-1-yl- methyl)-chloracetanilid vom Schmelzpunkt 140,5°C.
Zu einer Lösung von 93g (1 Mol) Anilin, 250 ml Methylenchlorid, 2 ml Dimethylbenzylamin und 150g wasserfreiem Magnesiumsulfat tropft man bei 0°C unter Rühren innerhalb 1 Stunde 144g (2 Mol)Isobutyraldehyd zu. Man läßt 2-5 Stunden bei 0 bis 100C nachrühren, filtriert und wäscht den Rückstand zweimal mit 200 ml Methylenchlorid nach. Die vereinigten organischen Phasen werden im Vakuum bei 30 bis 40°C vom Lösungsmittel befreit. Man erhält 155g rohes N-Isobutyliden-anilin, das direkt weiter umgesetzt wird.A solution of 93 g (1 mol) of aniline, 250 ml of methylene chloride, 2 ml of dimethylbenzylamine and 150 g of anhydrous magnesium sulfate is added dropwise at 0 ° C. with stirring over the course of 1 hour to 144 g (2 mol) of isobutyraldehyde. The mixture is stirred for 2-5 hours at 0 to 10 0 C, filtered and the residue is washed twice with 200 ml of methylene chloride to. The combined organic phases are freed from the solvent in vacuo at 30 to 40 ° C. 155 g of crude N-isobutylidene aniline are obtained, which is directly reacted further.
Die in der Stufe 2 erhaltene Reaktionsmischung wird bei 20 bis 30°C unter Rühren innerhalb von 30 Minuten zu einer Lösung von 170g (2,5 Mol) Pyrazol und 250 ml Methylenchlorid gegeben. Nach beendeter Zugabe läßt man 4 Stunden bei Raumtemperatur nachrühren. Anschließend wird die Reaktionsmischung auf eine gesättigte Lösung von Natriumhydrogencarbonat gegeben. Die organische Phase wird abgetrennt, mehrmals mit gesättigter Natriumhydrogencarbonatlösung gewaschen, über Natriumsulfat getrocknet und durch Abdestillieren des Lösunsgmittels eingeengt. Der verbleibende Rückstand wird aus Toluol/Ligroin umkristallisiert. Man erhält 122,5g (42 % der Theorie, bezogen auf in der Stufe 1 eingesetztes Anilin) N-(1-Pyrazol-1-yl-isobut-1-yl)-chloracetanilid vom Schmelzpunkt 75°C.The reaction mixture obtained in stage 2 is added to a solution of 170 g (2.5 mol) of pyrazole and 250 ml of methylene chloride at 20 to 30 ° C. with stirring within 30 minutes. When the addition is complete, the mixture is stirred for 4 hours at room temperature. The reaction mixture is then added to a saturated solution of sodium hydrogen carbonate. The organic phase is separated off, washed several times with saturated sodium bicarbonate solution and dried over sodium sulfate and concentrated by distilling off the solvent. The remaining residue is recrystallized from toluene / ligroin. This gives 122.5 g (42% of theory, based on the aniline used in stage 1) of N- (1-pyrazol-1-yl-isobut-1-yl) chloroacetanilide, melting point 75 ° C.
In analoger Weise werden die in der folgenden Tabelle 1 formelmäßig aufgeführten Endprodukte der Formel (XII) hergestellt.
Fntsprechend den Beispielen 1 bis 5 werden die in der folgenden Tabelle formelmäßig aufgeführten Zwischenprodukte der Formel (XV) erhalten.
In dem nachfolgenden Beispiel wird die nachstehend angegebene Verbindung als Vergleichssubstanz eingesetzt:
Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone
Emulgator 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Samen der Testpflanzen werden in normalen Boden ausgesät und nach 24 Stunden mit der Wirkstoffzubereitung begossen. Dabei hält man die Wassermenge pro Flächeneinheit zweckmäßigerweise konstant. Die Wirkstoffkonzentration in der Zubereitung spielt keine Rolle, entscheidend ist nur die Aufwandmenge des Wirkstoffs pro Flächeneinheit. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten:
- 0 %=keine Wirkung (wie unbehandelte Kontrolle)
- 100 %=totale Vernichtung
- 0% = no effect (like untreated control)
- 100% = total annihilation
Die erfindungsgemäß herstellbaren Wirkstoffe (XII-1) und (XV-7) zeigen in diesem Test eine bessere selektive Wirksamkeit als die aus dem Stand der Technik bekannte Substanz (A).In this test, the active ingredients (XII-1) and (X V -7) which can be prepared according to the invention show a better selective activity than the substance (A) known from the prior art.
Claims (11)
dadurch gekennzeichnet, daß man in einer 1. Stufe Aniline der Formel
mit Aldehyden der Formel
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines basischen oder dauren Katalysators umsetzt, dann in einer 2.Stufe die entstehenden Azomethine der Formel
mit Halogenacethalogeniden der Formel
gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und in einer 3. Stufe die entstehenden substituierten N-Halogenmethylhalogenacetanilide der Formel
direkt, oder gegebenenfalls nach vorheriger Isolierung, mit Azolen der Formel
gegebenenfalls in Gegenwart eines Verdünnungsmittels und in Gegenwart eines Säurebindemittels umsetzt, wobei die Azole der Formel (XVIII) auch in Form ihrer Alkalimetallsalze eingesetzt werden können.1. Process for the preparation of substituted N-azolyl-methyl-haloacetanilides of the formula
characterized in that anilines of the formula
with aldehydes of the formula
if appropriate in the presence of a diluent and if appropriate in the presence of a basic or acid catalyst, then in a second stage the resulting azomethines of the formula
with haloacethalides of the formula
if appropriate in the presence of a diluent and in a third step the resulting substituted N-halomethylhaloacetanilides of the formula
directly, or optionally after prior isolation, with azoles of the formula
if appropriate in the presence of a diluent and in the presence of an acid binder, the azoles of the formula (XVIII) also being able to be used in the form of their alkali metal salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3011084 | 1980-03-22 | ||
| DE19803011084 DE3011084A1 (en) | 1980-03-22 | 1980-03-22 | METHOD FOR PRODUCING SUBSTITUTED N-AZOLYLMETHYL HALOGEN ACETANILIDES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0036544A1 true EP0036544A1 (en) | 1981-09-30 |
| EP0036544B1 EP0036544B1 (en) | 1984-01-25 |
Family
ID=6097983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81101699A Expired EP0036544B1 (en) | 1980-03-22 | 1981-03-09 | Method for the preparation of substituted n-azolyl-methyl-halogeno-acetanilides |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0036544B1 (en) |
| JP (1) | JPS56158767A (en) |
| BR (1) | BR8101685A (en) |
| DE (2) | DE3011084A1 (en) |
| DK (1) | DK126081A (en) |
| IL (1) | IL62430A0 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0088259A2 (en) * | 1982-02-17 | 1983-09-14 | Consortium für elektrochemische Industrie GmbH | Azolyl-pyrrolidinones, process for their preparation and their use as fungicides |
| WO2013104478A1 (en) * | 2012-01-13 | 2013-07-18 | Basf Se | Process for preparing acetanilides |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT382870B (en) * | 1982-02-09 | 1987-04-27 | Sandoz Ag | Process for the preparation of novel chloroacetamides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1542950B2 (en) * | 1963-08-22 | 1975-08-07 | Monsanto Co., St. Louis, Mo. (V.St.A.) | Substituted acetanilides, processes for their preparation and herbicidal compositions containing these compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2835156A1 (en) * | 1978-08-10 | 1980-02-14 | Bayer Ag | SUBSTITUTED N-PYRAZOLYL METHYL HALOGEN ACETANILIDES, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
| DE2835157A1 (en) * | 1978-08-10 | 1980-02-21 | Bayer Ag | METHOD FOR PRODUCING N-SUBSTITUTED ALPHA -HALOGENACETANILIDES |
-
1980
- 1980-03-22 DE DE19803011084 patent/DE3011084A1/en not_active Withdrawn
-
1981
- 1981-03-09 EP EP81101699A patent/EP0036544B1/en not_active Expired
- 1981-03-09 DE DE8181101699T patent/DE3162002D1/en not_active Expired
- 1981-03-19 JP JP3882981A patent/JPS56158767A/en active Pending
- 1981-03-19 IL IL62430A patent/IL62430A0/en unknown
- 1981-03-20 BR BR8101685A patent/BR8101685A/en unknown
- 1981-03-20 DK DK126081A patent/DK126081A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1542950B2 (en) * | 1963-08-22 | 1975-08-07 | Monsanto Co., St. Louis, Mo. (V.St.A.) | Substituted acetanilides, processes for their preparation and herbicidal compositions containing these compounds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0088259A2 (en) * | 1982-02-17 | 1983-09-14 | Consortium für elektrochemische Industrie GmbH | Azolyl-pyrrolidinones, process for their preparation and their use as fungicides |
| EP0088259A3 (en) * | 1982-02-17 | 1984-08-29 | Consortium für elektrochemische Industrie GmbH | Azolyl-pyrrolidinones, process for their preparation and their use as fungicides |
| WO2013104478A1 (en) * | 2012-01-13 | 2013-07-18 | Basf Se | Process for preparing acetanilides |
| US9079862B2 (en) | 2012-01-13 | 2015-07-14 | Basf Se | Process for preparing acetanilides |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8101685A (en) | 1981-09-22 |
| EP0036544B1 (en) | 1984-01-25 |
| DK126081A (en) | 1981-09-23 |
| IL62430A0 (en) | 1981-05-20 |
| DE3011084A1 (en) | 1981-10-01 |
| DE3162002D1 (en) | 1984-03-01 |
| JPS56158767A (en) | 1981-12-07 |
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